Vinyl end-capped polyimide oligomers

ABSTRACT

The products of the invention are vinyl end-capped oligomers which are prepared from 2,4-bis (p-aminobenzyl) aniline and a vinyl substituted aromatic monoamine, the principal component of which is the compound whose structure is shown in FIG. 3. The products are prepared from either of two (2) precursors. The first precursor is a compound whose structure is shown in FIG. 2 and which is prepared from 2,4-bis (p-aminobenzyl) aniline, a dianhydride of an aromatic tetracarboxylic acid such as 3,3&#39;4,4&#39;-benzophenonetetracarboxylic acid (BTDA) and a vinyl substituted aromatic monoamine, such as 3-aminophenyl-ethylene (APE). The second precursor is a complex amine salt having the structure shown in FIG. 6 and which is prepared from 2,4-bis-(p-aminobenzyl) aniline, a dialkyl ester of BTDA and APE.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 3,845,018 and U.S. Pat. No. 3,879,349 disclose certain acetylene end-capped polyimide oligomers. Moldings prepared from such resin have excellent physical properties which are largely retained at temperatures as high as 316° C. (600° F.).

The polyimides disclosed in these patents must be prepared from aromatic diamines of specific structures to obtain the desired high temperature performance properties. Unfortunately such amines are difficult to synthesize and are expensive. The synthesis also requires employment of aminoarylacetylenes which are difficult to synthesize and are expensive. As a consequence, the polyimides of U.S. Pat. No. 3,845,018 and U.S. Pat. No. 3,879,349 can be employed only where critical operational requirements can justify unusually high material costs.

For the above reasons, there is a need in the art for polyimides having good high temperature performance properties which can be prepared from polyamines that can be more easily synthesized and be made available at lower cost.

SUMMARY OF THE INVENTION

The products of the invention are vinyl end-capped oligomers which are prepared from an aromatic triamine such as 2,4-bis(p-aminobenzyl) aniline and a vinyl substituted aromatic monoamine, the principal component of which is the compound whose structure is shown in FIG. 3. The invention also is directed to two (2) precursors of the vinyl end-capped oligomers. The first precursor is a reaction product of an aromatic triamine and a vinyl substituted aromatic monoamine containing amic-acid groups, the principal component of which is the compound whose structure is shown in FIG. 2. The second precursor is a complex amine salt prepared in part from an aromatic triamine and a vinyl substituted aromatic monoamine, the principal component of which is the salt shown in FIG. 6.

THE DRAWINGS

FIG. 1 is the chemical structure of an intermediate compound employed to prepare the compound of FIG. 2.

FIG. 2 is the chemical structure of a precursor of the end-capped polyimides of FIG. 3.

FIG. 3 is the structure of the end-capped polyimides of the invention.

FIG. 3' is the structure of a preferred species of the generic end-capped polyimides illustrated in FIG. 3.

FIG. 4 is a low polymer of the product of FIG. 3'.

FIG. 5 is the chemical structure of an intermediate compound employed to prepare the compound of FIG. 6.

FIG. 6 is the chemical structure of a second precursor of the end-capped polyimides of FIG. 3.

DETAILED DESCRIPTION OF THE INVENTION

The vinyl end-capped polyimide oligomers can be prepared by two alternate synthesis methods subsequently designated as Synthesis Method A and Synthesis Method B.

Synthesis Method A

In the first step of this method, substantially three (3) mols of a dianhydride of an aromatic tetracarboxylic acid such as 3,3'4,4'benzophenonetetracarboxylic acid dianhydride (BTDA) are reacted with one (1) mol of an aromatic triamine in a selected class of solvents under controlled temperature conditions. Letting the structure of the dianhydride be represented as: ##STR1## and the structure of the triamine be represented as ##STR2## (the structure of R and R' being defined infra) the principal product of this first reaction has the structure shown in FIG. 1.

In the second step of this method, a vinyl substituted aromatic monoamine such as 3-aminophenyl ethylene (APE) is reacted with the reaction product of the first step of the process. Letting the structure of the vinyl substituted aromatic monoamine be represented as:

    H.sub.2 N--R"

(the structure of R" being defined infra), the principal product of the second reaction has the structure shown in FIG. 2.

In the third step of this method, the reaction product of the second step is subjected to a dehydration reaction of the type known and reported in the literature to effect ring closure of the amic-acid groups to form imide groups. The product of this step is the desired vinyl end-capped polyimide oligomer. The principal compound of the oligomer has the structure shown in FIG. 3. FIG. 3' shows the structure of the preferred species in which aromatic triamine employed in the synthesis in 2,4-bis(p-aminobenzyl)aniline (BPABA).

In the first step of the process, the dianhydride of the aromatic tetracarboxylic acid employed will have the structure of formula 1: ##STR3## where R has the structure: ##STR4## where X is ##STR5## or a bond. Examples of suitable compounds conforming to formula 1 include 3,3'4,4'-benzophenonetetracarboxylic acid dianhydride (BTDA), 3,3'4,4'diphenyl tetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis(3,4-carboxyphenyl) sulfone dianhydride, and the like. Such compounds are known and reported in the art.

The solvent employed should be one having good solvent power for the dianhydride of formula 1 and the first intermediate product shown in FIG. 1. Suitable solvents include N-methyl-2-pyrrolidone (NMP), cyclohexanone, diethyl carbonate and gamma-butyrolactone. NMP is the solvent of choice.

In the first step of the process, the dianhydride of formula (1) such as BTDA* is heated in one of the limited class of solvents previously described, preferably NMP, to prepare a solution containing a minimum of at least 17 weight % of BTDA. In this step of the process, the BTDA should be dissolved in the solvent at a temperature substantially higher than will be employed in subsequent steps of the process. Typically the BTDA will be dissolved in the solvent at a temperature of at least 150° C. and temperatures as high as 200° C. can be employed. By operating at these temperatures, it is possible to dissolve substantially more BTDA than will dissolve at the reaction temperatures employed in subsequent steps of the process. Upon cooling such solutions to the lower temperatures subsequently employed in the reactions, it is observed that the BTDA does not precipitate but stays in solution, presumably by reason of the super cooling.

The quantity of BTDA dissolved in the solvent will be dictated by the solids desired in the intermediate solution and also by the quantity of solvent (if any) employed to dissolve the reactants employed in subsequent steps of the process. It is possible to prepare NMP solutions containing up to 50 weight % BTDA which remain liquid at a temperature of 50° C. It is preferred to prepare a solution containing a minimum of 17 weight % BTDA.

In the second step of the process, the hot solution of BTDA is cooled to the temperature which will be employed in the subsequent steps of the process. This temperature will be influenced by a multitude of factors. Temperatures as low as about 25° C. are sufficiently high to run the subsequent reactions, but somewhat higher temperatures may be required to maintain a sufficient quantity of BTDA in solution. Solutions of BTDA are quite viscous and increasing the temperature provides easier mixing of the reactants. Temperatures above 100° C. should be avoided, as the use of high temperatures promotes imidization of the amic acid groups present in the structure shown in FIG. 1. Such imidization is undesirable as the imide group containing products have reduced solubility in the solvent and tend to precipitate from solution. A preferred temperature range for this step of the process is about 30°-100° C. and more especially about 45°-75° C.

After the BTDA solution has been adjusted to the appropriate temperature, the aromatic triamine is added in small increments to the BTDA solution with stirring. The aromatic triamine will be added in a quantity corresponding to 0.33 molar portion per molar portion of BTDA. This reaction proceeds readily at the prevailing temperature and provides an intermediate product consisting almost exclusively of a chemical having the structure set forth in FIG. 1.

The aromatic triamine employed has the structure: ##STR6## In the above formula, R' represents an aryl group. Aryl in turn, for the purpose of this application, is defined as containing at least one 6-membered ring containing benzenoid unsaturation. Where aryl contains two or more 6-membered rings, the rings can be joined by sharing a common pair of carbon atoms, e.g., as in a naphthyl grouping, or by being joined by a valence bond, e.g., as in a biphenyl grouping, or by a linking carbon, oxygen, or sulfur atom of the type defined as X in formula (1). The ring preferably will contain only carbon atoms, but also may contain up to three nitrogen atoms. Examples of suitable nitrogen-containing rings include azine rings, diazine rings (1,2 or 1,3 or 1,4 rings), and the various isomeric triazine rings. Examples of suitable amines of this class include the isomeric tri(amino) substituted benzenes, toluenes, and xylenes, the tri(amino) substituted naphthalenes and biphenyls, and the like. The preferred aromatic triamine is 2,4-bis (p-aminobenzyl) aniline (BPABA). Examples of triamines in which the aryl group contains one or more nitrogen atoms include 2,4,6-triaminopyridine, 2,4,6-triamino- 1,3-pyrimidine, and 2,4,6-triamino-1,3,5-triazine (melamine).

The .[.binyl.]. .Iadd.vinyl .Iaddend.substituted aromatic monoamine employed in the next step of the process has the structure:

    H.sub.2 N--R"tm (3)

where R" is an aryl group such as a phenylene group, a naphthylene group, ##STR7## where X is as previously defined and one (1) valence bond of the aryl group bears a substituent having the structure:

    --CH═CH.sub.2

Examples of suitable compounds of this class include vinyl aniline, aminophenyl ethylene (APE) in alternate nomenclature, the alkyl substituted vinyl substituted anilines such as the vinyl substituted toluidines and xylidines, the vinyl substituted naphthylamines, the vinyl substituted monoamino substituted biphenyls and the like. Aminophenyl ethylene (APE) is the preferred species. Certain of the vinyl substituted aromatic monoamines are known compounds reported in the literature. Other of the compounds can be prepared by classical synthesis routes from commercially available materials.

The vinyl substituted aromatic monoamine, preferably 3-aminophenylethylene (APE), is added in small increments with stirring to the solvent solution of the intermediate product prepared in the previous step of the process. APE is a liquid at ambient temperature and can be added in neat form or as a concentrated solution in the solvent employed in the earlier steps of the process. Good stirring and cooling should be provided to maintain a reaction temperature within the limits previously described. The APE is added in a molar quantity equivalent to the molar quantity of BTDA charged to the first step of the process. The reaction product is a solution of a chemical consisting almost exclusively of the structure shown in FIG. 2.

The product of the preceding step can be converted to the desired vinyl end-capped polyimide oligomer by effecting ring closure of the amic acid groups by a dehydration reaction. Such methods are reported in the art, particularly the Barie patent U.S. Pat. No. 4,097,456 whose descriptions are incorporated herein by reference.

Synthesis Method B

In the first step of this method substantially three (3) mols of certain diesters of an aromatic tetracarboxylic acid such as a dialkyl ester of 3,3'4,4'benzophenonetetracarboxylic acid dianhydride (BTDA) are reacted with one (1) mol of 2,4-bis(p-aminobenzyl) aniline* in a suitable solvent to form an amine salt. Letting the dialkyl ester of the aromatic carboxylic acid be represented as: ##STR8## (the structure of R and R'" being defined infra), the principal product of this first reaction has the structure shown in FIG. 5.

In the second step of this method, a vinyl substituted aromatic monoamine of formula (2) such as 3-aminophenylethylene (APE) is reacted with the reaction product of the first step of the process to form a complex amine salt whose principal component has the structure shown in FIG. 6.

In the third step of this method, the reaction product of the second step is heated to effect a ring closure to form imide groups. The product of this step is the desired vinyl end-capped polyamide oligomer.

The dialkyl esters of the aromatic tetracarboxylic acid employed in the first step of the process have the formula: ##STR9## where R has the same meaning as in formula (1) and where R'" is the moiety derived from a suitable alcohol, preferably an alkanol containing up to about 5 carbon atoms. It will be recognized that 3-position isomers are possible for each diester, all of which are functional equivalents in the present invention. The desired dialkyl esters can be prepared by reacting 1 molar portion of a dianhydride of formula (1), e.g., BTDA, with 2-molar portions of a lower alkanol containing up to 5 carbon atoms. An excess of the alkanol can be used as the reaction solvent and only the desired dialkyl ester will be formed.

In the first step of the process, the diester of the aromatic tetracarboxylic acid, e.g., a diester of BTDA, is reacted with the BPABA in a suitable solvent. Typically, the solvent employed will be the alkanol from which the diester is prepared. If desired, however, other lower alkanols containing up to about 5 carbon atoms and lower ethers containing up to about 6 carbon atoms can be employed, preferably such solvents having atmospheric boiling points of less than 150° C. If desired, mixtures of solvents can be employed, including mixtures of an alcohol or an ether with water. Each of the chemicals is dissolved in the minimum required quantity of the solvent.

This first reaction preferably is run by adding the BPABA solution in small increments to the solution of the diester. Good stirring is provided so that localized high concentrations of BPABA are avoided for reasons essentially similar to those noted respecting the first step of Synthesis Method A previously discussed.

In the next step of the process, a vinyl substituted aromatic amine of formula (3), such as APE, is added in small increments with stirring to the solvent solution of the intermediate product produced in the previous step of the process. The majority of the vinyl substituted aromatic monoamines are liquids at ambient temperature and can be added to reaction in neat form, or as a concentrated solution in the same solvent employed in the earlier steps of the process.

In the final step of this method, the reaction product of the second step is heated to effect a ring closure to form imide groups. This step preferably is carried out employing the techniques disclosed in the pending Antonoplos et al application Ser. No. 956,708, filed Nov. 1, 1978, which disclosure is incorporated herein by reference. The Antonoplos et al application is owned by the assignee of the present application.

Structure and Utility of Products

As previously noted, the vinyl end-capped polyimide oligomers of the invention consist principally--virtually exclusively if proper synthesis procedures are followed--of the compound having the structure shown in FIG. 3. In the initial synthesis step of Synthesis Method A, the dianhydride of formula (1) is difunctional and BPABA is trifunctional. As a consequence, some small percentage of low polymers of the compound shown in FIG. 1 can be prepared, these polymers being principally dimers and trimers. As a consequence, when the ethylene substituted aromatic monoamine of formula (2) is reacted with such polymers, low polymers of the compound shown in FIG. 2 also are prepared. Finally, when such polymers are converted to the ultimately-desired imides, low polymers of the compound shown in FIG. 3 or 3' also are prepared. The structure of products of FIG. 3' is shown in FIG. 4 where R and R" have the previously-defined meaning and n and n' are small integers having values such as 1, 2, and 3.

It has been observed that up to 50 mol % of the vinyl-substituted aromatic monoamine employed in preparing the products of the invention can be replaced with a corresponding aromatic monoamine that is free of an ethylene substituent. These modified products have structures corresponding to those shown in FIGS. 2, 3, 4, and 6, except that up to 50 mol % of the terminal ethylene groups --CH═CH₂ are replaced with a hydrogen atom. Only a small sacrifice in properties is suffered, while the cost of manufacture is reduced substantially.

The vinyl end-capped oligomers of the invention can be molded and heat cured to provide moldings having excellent strength, which strength is retained to a surprising degree even after the molded articles are heated for extended periods of time at elevated temperatures, e.g., 500 or more hours at 315° C. (600° F.). Moreover, the products, before being cured, have adequate flow to be processed satisfactorily. Free radical generating polymerization initiators can be employed to accelerate cross-linking, but are not required.

In addition to being employed to prepare moldings, the vinyl end-capped polyimide oligomers can be used to lay down tough coatings on substrates such as metals and to prepare laminates and/or composite structures. To prepare such structures, a web of inorganic fibers such as glass, quartz, graphite fibers or the like, is impregnated with a solution containing the polyimide solids. The impregnated web then is heated to modest temperatures to cross-link the vinyl end-capped oligomer.

Where it is desired to prepare coatings, laminates or composites, it is possible and usually desirable to prepare such compositions from one of the precursors of the polyimide oligomer. Either of the two previously described precursors, i.e., of the structure shown in FIG. 2 or FIG. 6, can be employed. When the precursors are heated, they form the polyimide structure shown in FIG. 3 and upon further heating form cross-linked products. The advantage of employing the precursors is that they have a much higher solubility in solvents. As a consequence, higher solids levels can be incorporated into the laminate or composite. It is possible to prepare solutions which contain at least 30 weight % of the product of FIG. 2 in solvents such as NMP. It is possible to prepare solutions containing at least 50 weight % of the product of FIG. 6 in solvents such as the 1-5 carbon alkanols.

Where desired, the intermediates of FIG. 6 can be converted to a solid state for storage or shipment by careful spray drying employing the conditions set forth in the Antonoplos et al application Ser. No. 956,708, filed Nov. 1, 1978, and earlier incorporated herein by reference. These solids then can be dissolved in a suitable solvent of the type previously described to prepare coating and/or laminating solutions.

When used as coating compositions, the precursor solution should be laid down on the substrate and heat cured at temperatures of 175° C. or higher. To prepare laminates, the desired web should be impregnated with a precursor solution and heated to an elevated temperature for a time sufficient to convert the precursor solids to imides and liberate water. Drying the impregnated web for 60 minutes at 150° C. or 80 minutes at 135° C. in a circulating air oven is usually sufficient. The dried webs then can be laid up and heated under pressure to cross-link the resin solids. Modest pressures of the order of 15-200 psig are sufficient. Curing temperatures of the order of 177°-260° C. and preferably 195°-220° C. are employed for curing times of the order of 1-12 hours. Optimum properties are developed by post curing the laminates for periods of 16-48 hours at temperatures of about 260°-375° C.

The following examples are set forth to illustrate the principle and practice of the invention to those skilled in the art. Where parts and percentages are set forth, unless otherwise noted, they are parts and percentages expressed on a weight basis.

EXAMPLE 1 Part A

Charge 60 ml of NMP and 48.3 grams (0.15 mol) of BTDA to a reaction vessel equipped with a high-powered stirrer. Heat the mixture to 150° C. with stirring to dissolve all of the BTDA and then cool to 60° C. Add a solution of 15.6 grams (0.05 mol) of BPABA dissolved in 20 ml of NMP dropwise over a period of 1 hour. Cool the vessel to maintain the reaction temperature at about 60° C. The product solids will consist principally of a compound having the structure shown in FIG. 1.

Part B

Add 17.9 grams (0.15 mol) of APE dropwise with stirring over a priod of 1 hour to the solution of Part A while cooling the vessel to maintain a reaction temperature of about 60° C. The product solids will consist principally of a compound having the structure shown in FIG. 2. The NMR spectrum of the product will show no detectable concentration of imide groups.

Part C

Charge the product of Part B and 300 ml of toluene to a flask equipped with a Dean-Stark Trap. Heat to reflux to effect a ring closure to form imide groups and remove the liberated water as an azeotrope. In about 4 hours the theoretical quantity of water is collected. Recover the product by pouring it into about 2 liters of ethanol to precipitate a product consisting principally of a compound having the structure shown in FIG. 3'. The yield is essentially quantitative. Moldings prepared from this product have high-temperature strength properties essentially similar to moldings prepared from the products exemplified in U.S. Pat. No. 3,845,018 and U.S. Pat. No. 3,897,349.

EXAMPLE 2 Part A

Charge 30 grams (0.66 mol) of ethanol and 49.3 grams (0.15 mol) of BTDA to a reaction vessel equipped with a high-powered stirrer. Heat the mixture to reflux with stirring until all of the BTDA is esterified to form the diethyl ester of BTDA. The solution, when cooled to ambient temperature, has a viscosity of about 2,500 cps at 25° C. Add a solution of 15.6 grams (0.05 mol) of BPABA dissolved in 80 grams of ethanol, dropwise with stirring, over a period of about 15 minutes. The solution thus prepared will contain about 35 weight % solids. Distill approximately 80 grams of ethanol to prepare a solution containing about 75 weight % solids. The product solids consist principally of an amine salt having the structure shown in FIG. 5.

Part B

Add a total of 17.9 grams (0.15 mol) of APE dropwise with stirring over a period of 15 minutes to the product of Part A. The product contains about 78 weight % solids and has a viscosity of about 75,000 cps at 25° C. The product solids consist principally of an amine salt having the structure shown in FIG. 6.

Part C

Inject the product of Part B onto the rotating flask of a rotary evaporator heated to about 90° C. and operated at about 1 mm of Hg. This product is partially imidized. Heat this product for 20 hours at 130° C. in a vacuum oven operated at 1 mm of Hg. to complete the imidization reaction. The product is essentially identical to the product of Example 1, Part C.

EXAMPLE 3

Impregnate six-inch squares of 181 E glass cloth (with an A-1100 finish) with the resin solution of Example 1, Part B. Dry these samples for 30 minutes in a circulating air oven at 150° C. Extract a specimen of the dried fabric with NMP for chromatographic, NMR and I.R. analysis. The extracted product will contain no evidence of carboxyl groups, thus indicating that all of the amic acid groups have been converted to imide groups.

EXAMPLE 4

Lay up six pieces of 181 E glass fabric from Example 3 in the form of a laminate, place in a press under a pressure of 200 psig, and heat for two hours at 250° C. The laminate will be medium brown in color and contain approximately 25 weight % resin. Postcure the laminate for four hours at 650° F. (343° C.) and then an additional 15 hours at 700° F. (370° C.). No blisters or voids will be present in the postcured laminate.

EXAMPLE 5

Impregnate six-inch squares of 181 E glass cloth fabric (with an A-1100 finish) with the resin solution of Example 2, Part B. Dry these samples overnight at room temperature and then heat for 30 minutes in a circulating air oven at 190° C. The dried fabric will contain about 35 weight % resin solids.

When an attempt is made to extract resin solids from the dried glass fabric with ethanol, only a small percentage of the solids are extracted. This fact suggests that the resin solids have undergone a chemical reaction during the drying step. When the dried glass fabric is extracted with N-methyl-2-pyrrolidone (NMP), an extract is recovered which is soluble to the extent of about 3 weight % in the NMP at room temperature. No detectable quantity of carboxylic acid protons will be present in the spectrum. The IR spectrum of the NMP extract is essentially identical to the product of Example 1, Part C.

EXAMPLE 6 Part A

Graphite tapes 5" wide are impregnated with the resin solution prepared in Example 2, Part B. The fibers are a commercial product sold under the name Celion 3000, have an O twist, and bear an NR 150-B2 surface size. The impregnated tapes are dried until the tapes contain 40 weight % resin solids. The prepregs are 2.5 mls thick. A laminate lay up is made from 32 plys with the prepregs all being aligned in one direction. The lay up is laminated by a vacuum bag technique with the assembly being heated from ambient temperature to 265° F. with the temperature being increased at a rate of about 5°/minute under a vacuum of 15 inches of Hg. The assembly is maintained for an additional 2-hour period under 15 inches of Hg. The pressure then is reduced to the maximum vacuum that can be drawn and the temperature is increased to 485° F. at a rate of about 7° F./minute. The laminate is held at 485° F. for an additional period of 2 hours. The laminate is cooled to room temperature over a period of 5 hours. The laminate is post cured by heating from room temperature to 650° F. at a rate of 5°-10° F./minute and then heating for 13 hours at 650° F. The temperature then is increased to 700° F. at a rate of 5°-10° F./minute. The temperature then is held at 700° F. for an additional 4 hours.

The Short Beam Shear, Flexural Strength, and Tangent Modulus of Elasticity, as determined by ASTM procedures at room temperature and at 600° F., are substantially as set forth in Table I.

                  TABLE I                                                          ______________________________________                                                      Room Temperature                                                  Property     Value         600° F. Value                                ______________________________________                                         Short Beam Shear                                                                             12 ksi       7 ksi                                               Flexural Strength                                                                           200 ksi       140 ksi                                             Tangent Modulus of                                                                          20,000,000 ksi                                                                               19,000,000 ksi                                      Elasticity                                                                     ______________________________________                                    

Part B

Specimens of the laminates prepared in Part A, when heated for 300 hours at 600° F., show a weight loss of only about 2%. 

What is claimed:
 1. A product selected from the group consisting of:A. An end-capped polyimide oligomer whose principal component has the structure: ##STR10## where R has the structure: ##STR11## where X is ##STR12## or a bond; where R' is an aryl group; and where R" is an aryl group bearing a substituent having the structure:

    --CH═CH.sub.2 ;

B. A first precursor of an end-capped polyimide oligomer of (A) whose principal component has the structure: ##STR13## where R, R', and R" are defined as above; C. A second precursor of an end-capped polyimide oligomer of (A) whose principal component has the structure: ##STR14## where R, R', and R" are as defined above, and where R'" is the alcohol moiety from which the diester of the aromatic tetracarboxylic acid was prepared.
 2. An end-capped polyimide oligomer whose principal component has the structure: ##STR15## where R has the structure: ##STR16## where X is ##STR17## or a bond; where R' is an aryl group; and where R" is an aryl group bearing a substituent having the structure:

    --CH═CH.sub.2.


3. A precursor of an acetylene end-capped polyimide oligomer of claim 1, the principal component of said precursor having the structure: ##STR18## where R has the structure: ##STR19## where X is ##STR20## or a bond; where R' is an aryl group; and where R" is an aryl group bearing a substituent having the structure:

    --CH═CH.sub.2.


4. A precursor of an end-capped polyimide oligomer of claim 1, the principal component of said precursor having the structure: ##STR21## where R has the structure: ##STR22## where X is ##STR23## or a bond; where R' is an aryl group; where R" is an aryl group bearing a substituent having the structure:

    --CH═CH.sub.2

and where R'" is the alcohol moiety from which the diester of the aromatic tetracarboxylic acid was prepared.
 5. A product of claim 1, 2, 3 or 4 in which R' has the structure: ##STR24##
 6. A product of claim 1, 2, 3 or 4 in which R has the structure: ##STR25##
 7. A product of claim 1, 2, 3 or 4 in which R has the structure: ##STR26## and where R' has the structure: ##STR27##
 8. A product of claim 1, 2, 3 or 4 in which R has the structure: ##STR28## R' has the structure: ##STR29## and R" has the structure: ##STR30##
 9. A coating and laminating varnish consisting essentially of a product of claim 3 dissolved in a solvent selected from the group consisting of N-methyl-2-pyrrolidone, cyclohexanone, diethyl carbonate, and gamma-butyrolactone.
 10. A coating and laminating varnish consisting essentially of a product of claim 4 dissolved in a solvent having an atmospheric boiling point of less than about 150° C. and selected from the group consisting of lower alkanols containing up to about 5 carbon atoms, lower ethers containing up to about 6 carbon atoms, and mixtures thereof.
 11. A product of claim 1, 2, 3, 4, 9, or 10 in which up to 50 mol % of the terminal --CH═CH₂ groups of R" is replaced with a hydrogen atom.
 12. A process for preparing a product of claim 3 which consists essentially of:A. Dissolving at least 17 weight % of an aromatic tetracarboxylic acid dianhydride in a solvent at a temperature of at least 60° C., B. Maintaining a solution of step (A) containing substantially 1 molar portion of said aromatic tetracarboxylic acid dianhydride at a temperature in a range of about 30°-100° C. and adding substantially 0.33 molar portion of an aromatic triamine thereto, and C. Adding substantially 1.0 molar portion of a vinyl substituted aromatic monoamine to the product of step (B); said aromatic tetracarboxylic acid dianhydride having the formula: ##STR31## where R has the structure: ##STR32## where X is ##STR33## or a bond; said aromatic triamine having the formula: ##STR34## where R' is an aryl group; and said vinyl substituted aromatic monoamine having the formula:

    H.sub.2 N--R"--CH.tbd.CH.sub.2

where R" is an aryl group; and the solvent employed in step (A) is selected from the group consisting of N-methyl-2-pyrrolidone, cyclohexanone, diethyl carbonate, and gamma-butyrolactone.
 13. A process for preparing a product of claim 3 which consists essentially of:A. Adding, with stirring, a solution containing substantially 0.33 molar portion of an aromatic triamine to a solution containing substantially 1.0 molar portion of a dialkyl ester of an aromatic tetracarboxylic acid, and B. Adding substantially 1.0 molar portion of a vinyl substituted aromatic monoamine to the solution of (A);the dialkyl ester of the aromatic tetracarboxylic acid employed in step (A) having the formula: ##STR35## where R has the structure: ##STR36## where X is ##STR37## or a bond; said aromatic triamine having the formula: ##STR38## where R' is an aryl group; and said vinyl substituted aromatic monoamine having the formula:

    H.sub.2 N--R"--CH═CH.sub.2

where R" is an aryl group; the solvent employed in Step (A) having an atmospheric boiling point of less than about 150° C. and is selected from the group consisting of lower alkanols containing up to about 5 carbon atoms, lower ethers containing up to about 6 carbon atoms, and mixtures thereof.
 14. A process of claim 12 or 13 in which R' has the structure: ##STR39##
 15. A process of claim 12 or 13 in which R has the structure: ##STR40##
 16. A process of claim 12 or 13 in which R has the structure: ##STR41## and where R' has the structure: ##STR42##
 17. A process of claim 12 or 13 in which R has the structure: ##STR43## and where R' has the structure: ##STR44## and R" has the structure: ##STR45## 